CN109402578B - Method for preparing high-entropy alloy coating based on reactive magnetron sputtering technology - Google Patents
Method for preparing high-entropy alloy coating based on reactive magnetron sputtering technology Download PDFInfo
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- CN109402578B CN109402578B CN201910017536.7A CN201910017536A CN109402578B CN 109402578 B CN109402578 B CN 109402578B CN 201910017536 A CN201910017536 A CN 201910017536A CN 109402578 B CN109402578 B CN 109402578B
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- 238000001755 magnetron sputter deposition Methods 0.000 title claims abstract description 54
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 45
- 239000000956 alloy Substances 0.000 title claims abstract description 45
- 239000011248 coating agent Substances 0.000 title claims abstract description 45
- 238000000576 coating method Methods 0.000 title claims abstract description 45
- 238000005516 engineering process Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 39
- 238000000498 ball milling Methods 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 29
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 28
- 239000010959 steel Substances 0.000 claims abstract description 28
- 229910052786 argon Inorganic materials 0.000 claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 238000004140 cleaning Methods 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 238000010849 ion bombardment Methods 0.000 claims abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 38
- 239000007789 gas Substances 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 238000004544 sputter deposition Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 238000005275 alloying Methods 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000007514 turning Methods 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000003801 milling Methods 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 5
- 229910000838 Al alloy Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 150000004767 nitrides Chemical class 0.000 description 8
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 238000007781 pre-processing Methods 0.000 description 4
- 238000005253 cladding Methods 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention discloses a magnetron sputtering technology based on reactionThe preparation method of high-entropy alloy coating includes removing oil stain on the surface of steel substrate, cleaning the steel surface by ion bombardment in magnetron sputtering equipment, ball-milling and mixing single metal powder Cr, Cu, Fe, Ni and Al in proportion, sintering under pressure to obtain high-entropy alloy target, placing the target on DC cathode of magnetron sputtering equipment, and coating Ar and N on the DC cathode2Carrying out magnetron sputtering on the steel substrate by using magnetron sputtering equipment in mixed atmosphere due to N2The ionization ratio of the aluminum alloy is high, an AlN and CrN reinforced high-entropy alloy coating can be formed on the surface of a steel matrix, and the coating has good wear resistance and corrosion resistance.
Description
Technical Field
The invention belongs to the field of surface treatment, and particularly relates to a method for preparing a high-entropy alloy coating by adopting a magnetron sputtering technology.
Background
The low-carbon steel has lower strength and hardness, and better plasticity and toughness. Therefore, the cold-formability is excellent, and the cold-formability can be performed by a method such as crimping, bending, or pressing. In addition, the steel has good weldability and thus has wide application, but the poor surface wear resistance and corrosion resistance limit the application. The high-entropy alloy has excellent performances such as high strength, high hardness, high corrosion resistance, high wear resistance, high toughness and the like which cannot be compared with the traditional alloy, and the hardness and the wear resistance of the high-entropy alloy can be further improved by adding a certain reinforcing phase. The CrN and AlN phases have excellent thermal stability, higher hardness, good wear resistance and corrosion resistance, and can be used as a reinforcing phase for preparing a coating. The coating can be prepared by adopting the technologies of high-energy beam cladding and the like, and has good bonding performance with a matrix, but the coating has large deformation and difficult control of components due to the high temperature heated by the high-energy beam in the cladding process, and can only be used in the occasions of wear resistance, and further machining is needed in the use of precise parts.
The magnetron sputtering method has the characteristics of low temperature of the substrate, small damage to the substrate and the like, so the magnetron sputtering method is adopted to form the coating by utilizing the characteristic that the nitride reinforcing phase is formed in the sputtering process, the reduction of the coating stress is facilitated, the binding force of the coating is improved, and the N is improved in the reactive sputtering process2The activity of N is enhanced, the chemical reaction is improved, and the proportion of the enhanced phase is increased.
The nitride enhanced high-entropy alloy coating is deposited on the low-carbon steel substrate, the characteristics of high hardness, high wear resistance and high toughness of the high-entropy alloy can be fully utilized, elements such as Cr, Ni and Fe can well improve the binding force between the coating and the low-carbon steel, and the nitride can improve the wear resistance, hardness and the like of the coating.
Disclosure of Invention
Aiming at the defects of poor wear resistance and corrosion resistance of low-carbon steel, the wear resistance and corrosion resistance of the low-carbon steel are improved by magnetron sputtering, and the method can be used for improving the wear resistance of high-precision parts, and comprises the following process steps:
the method comprises the following steps of firstly, preprocessing the surface of a precoated workpiece, wherein the material is steel generally, grinding the surface of the workpiece by using a grinding wheel or abrasive paper to remove rust, burrs and flashes, and removing oil stains on the surface by using acetone.
Alloying the single-substance metal powder Cr, Cu, Fe, Ni and Al by adopting a ball-milling mixing process, wherein the purity of each single-substance metal powder is 99.5-100%, and the particle size of the powder is 30-120 mu m; the mass ratio of Cr, Cu, Fe, Ni and Al is 1-1.1: 1.2-1.3: 1.2-1.4: 1.3-1.5: 0.5-0.6, a steel ball milling tank is used for ball milling and mixing, the mass ratio of grinding balls to metal powder is 2.6-3: 1, a vacuum valve is opened after sealing, vacuum pumping is carried out for 20-30 minutes, then the steel ball milling tank is placed into a planetary ball mill, the rotating speed is 260-320 r/min, the inversion frequency is 35-45 Hz, and the ball milling and mixing time is 60-80 minutes. And then, putting the powder into a pressure sintering furnace under the protection of argon, pressurizing to 200-350 MPa, keeping the sintering temperature at 950-1070 ℃ for 2-8 minutes, and sintering to obtain the high-entropy alloy target.
Thirdly, placing the high-entropy alloy target on a direct current cathode of the magnetron sputtering equipment, closing a vacuum chamber of the magnetron sputtering equipment, and vacuumizing to 2.1 × 10-2Pa~2×10-3And Pa, introducing the flow of the Ar gas-regulated gas flowmeter to stabilize the gas pressure within the range of 1-6 Pa, turning on a negative bias power supply, regulating the negative bias to the range of 450-900V, and performing ion bombardment glow cleaning on the pre-coated workpiece for 10-20 minutes.
And step four, starting a heater of the magnetron sputtering equipment to heat the precoated workpiece after cleaning, and introducing 10-45 liters/minute of argon and nitrogen mixed gas into the vacuum chamber, wherein the argon: the flow ratio of nitrogen is 1: 2.1-3.2, the working air pressure is kept at 0.3-4.5 Pa, the target spacing is kept at 30-65 mm, the temperature of the precoated workpiece is kept at 190-210 ℃, the substrate bias voltage is 0.3-0.4 kV, the sputtering current is 0.1-0.75A, and the magnetron sputtering time is 5-36 minutes.
And step five, obtaining the AlN and CrN enhanced AlCrCuFeNi high-entropy alloy coating after the reaction magnetron sputtering is finished.
The invention has the beneficial effects that:
(1) the process method adopts the high-entropy alloy as the matrix of the wear-resistant coating, so that the coating has higher toughness, strength and wear resistance.
(2) The invention adopts magnetron sputtering, has the advantages of low substrate temperature and small deformation, avoids the defects of high cladding temperature, and can be used for manufacturing high-precision wear-resistant parts.
(3) Is adopted in N2Reactive magnetron sputtering is carried out in the atmosphere, and fine nitride is dispersed and distributed on the coating, so that the wear resistance of the coating can be further enhanced.
Detailed Description
Example 1:
the invention adopts a reactive magnetron sputtering technology to prepare a high-entropy alloy coating, and the preparation method comprises the following process steps:
the method comprises the following steps of firstly, preprocessing the surface of a precoated workpiece, wherein the material is steel generally, the surface of the precoated workpiece is polished by a grinding wheel or abrasive paper to remove rust, burrs and flashes, and oil stains on the surface are removed by acetone;
alloying the single-substance metal powder Cr, Cu, Fe, Ni and Al by adopting a ball-milling mixing process, wherein the purity of each single-substance powder is 99.5-100%, and the particle size of the powder is 30-120 mu m; the method comprises the following steps of mixing Cr, Cu, Fe, Ni and Al in a mass ratio of 1:1.2:1.2:1.3:0.5 by ball milling in a steel ball milling tank, sealing, opening a vacuum valve to vacuumize for 20 minutes, putting the steel ball milling tank into a planetary ball mill at a rotating speed of 260 r/min and an inversion frequency of 35 Hz, and mixing the materials by ball milling for 60 minutes, wherein the mass ratio of grinding balls to metal powder is 2.6: 1. And then, putting the powder into a pressure sintering furnace under the protection of argon, pressurizing to 200MPa, keeping the temperature for 2 minutes at the sintering temperature of 950 ℃, and sintering to obtain the high-entropy alloy target.
Thirdly, placing the high-entropy alloy target on a direct current cathode of the magnetron sputtering equipment, closing a vacuum chamber of the magnetron sputtering equipment, and vacuumizing to 2.1 × 10-2And Pa, introducing the flow of the Ar gas-regulated gas flowmeter to stabilize the gas pressure within the range of 1-3 Pa, turning on a negative bias power supply, regulating the negative bias to the range of 450V, and performing ion bombardment glow cleaning on the pre-coated workpiece for 10 minutes.
And step four, starting a heater of the magnetron sputtering equipment to heat the precoated workpiece after cleaning, and introducing 10 liters/minute of argon and nitrogen mixed gas into the vacuum chamber, wherein the argon: the flow ratio of nitrogen is 1:3.2, the working air pressure is kept at 0.3Pa, the target spacing is kept at 30mm, the temperature of the precoated workpiece is kept at 190 ℃, the substrate bias voltage is 0.3 kV, the sputtering current is 0.1A-0.15A, and the magnetron sputtering time is controlled to be 5 minutes.
And step five, obtaining the AlN and CrN enhanced AlCrCuFeNi high-entropy alloy coating after the reaction magnetron sputtering is finished.
Experiments show that the wear-resistant high-entropy alloy coating can be obtained by adopting reactive magnetron sputtering, nitrides AlN and CrN in the coating are fine and uniform, the deformation of a steel matrix is small, and the wear-resistant high-entropy alloy coating can be used for high-precision wear-resistant occasions.
Example 2:
the invention adopts a reactive magnetron sputtering technology to prepare a high-entropy alloy coating, and the preparation method comprises the following process steps:
the method comprises the following steps of firstly, preprocessing the surface of a precoated workpiece, wherein the material is steel generally, the surface of the precoated workpiece is polished by a grinding wheel or abrasive paper to remove rust, burrs and flashes, and oil stains on the surface are removed by acetone;
alloying the single-substance metal powder Cr, Cu, Fe, Ni and Al by adopting a ball-milling mixing process, wherein the purity of each single-substance powder is 99.5-100%, and the particle size of the powder is 30-120 mu m; the method comprises the following steps of sealing a steel ball-milling tank, vacuumizing for 30 minutes by opening a vacuum valve after sealing, putting the steel ball-milling tank into a planetary ball mill at the rotating speed of 320r/min and the inversion frequency of 45Hz, and mixing the materials by ball milling for 80 minutes, wherein the mass ratio of Cr, Cu, Fe, Ni and Al is 1.1: 1.4:1.5: 0.6. And then, putting the powder into a pressure sintering furnace under the protection of argon gas, pressurizing to 350MPa, keeping the temperature for 8 minutes at the sintering temperature range of 1070 ℃, and sintering to prepare the high-entropy alloy target.
Thirdly, placing the high-entropy alloy target on a direct current cathode of the magnetron sputtering equipment, closing a vacuum chamber of the magnetron sputtering equipment, and vacuumizing to 5 × 10-3And Pa, introducing the flow of the Ar gas-regulated gas flowmeter to stabilize the gas pressure within the range of 6Pa, turning on a negative bias power supply, regulating the negative bias to the range of 900V, and carrying out ion bombardment glow cleaning on the pre-coated workpiece for 20 minutes.
And step four, starting a heater of the magnetron sputtering equipment to heat the precoated workpiece after cleaning, and introducing 45 liters/minute of argon and nitrogen mixed gas into the vacuum chamber, wherein the argon: the flow ratio of nitrogen is 1:3.2, the working pressure is kept at 4.5Pa, the target spacing is kept at 65mm, the temperature of the precoated workpiece is kept at 210 ℃, the substrate bias voltage is 0.4kV, the sputtering current is 0.65A-0.75A, and the time is 36 minutes.
And step five, obtaining the AlN and CrN enhanced AlCrCuFeNi high-entropy alloy coating after the reaction magnetron sputtering is finished.
Experiments show that the wear-resistant high-entropy alloy coating can be obtained by adopting reactive magnetron sputtering, nitrides AlN and CrN in the coating are fine and uniform, the deformation of a steel matrix is small, and the wear-resistant high-entropy alloy coating can be used for high-precision wear-resistant occasions.
Example 3:
the invention adopts a reactive magnetron sputtering technology to prepare a high-entropy alloy coating, and the preparation method comprises the following process steps:
the method comprises the following steps of firstly, preprocessing the surface of a precoated workpiece, wherein the material is steel generally, the surface of the precoated workpiece is polished by a grinding wheel or abrasive paper to remove rust, burrs and flashes, and oil stains on the surface are removed by acetone;
alloying the single-substance metal powder Cr, Cu, Fe, Ni and Al by adopting a ball-milling mixing process, wherein the purity of each single-substance powder is 99.5-100%, and the particle size of the powder is 30-120 mu m; the method comprises the following steps of mixing Cr, Cu, Fe, Ni and Al in a mass ratio of 1:1.3:1.4: 1.3:0.5 by ball milling in a steel ball milling tank, sealing, opening a vacuum valve to vacuumize for 25 minutes, putting the steel ball milling tank into a planetary ball mill at a rotating speed of 280 r/min, reversing frequency of 40 Hz, and mixing the materials by ball milling for 70 minutes, wherein the mass ratio of grinding balls to metal powder is 2.8: 1. And then, putting the powder into a pressure sintering furnace under the protection of argon, pressurizing to 300MPa, keeping the temperature for 6 minutes at the sintering temperature of 1020 ℃, and sintering to obtain the high-entropy alloy target.
Thirdly, placing the high-entropy alloy target on a direct current cathode of the magnetron sputtering equipment, closing a vacuum chamber of the magnetron sputtering equipment, and vacuumizing to 2 × 10-3And Pa, introducing the flow of the Ar gas-regulated gas flowmeter to stabilize the gas pressure within the range of 4 Pa, turning on a negative bias power supply, regulating the negative bias to the range of 600V, and carrying out ion bombardment glow cleaning on the pre-coated workpiece for 15 minutes.
And step four, starting a heater of the magnetron sputtering equipment to heat the precoated workpiece after cleaning, and introducing 25 liters/minute of argon and nitrogen mixed gas into the vacuum chamber, wherein the argon: the flow ratio of nitrogen is 1:3, the working pressure is kept at 2.5Pa, the target spacing is kept at 45mm, the temperature of the precoated workpiece is kept at 200 ℃, the substrate bias voltage is 0.35 kV, the sputtering current is 0.5A-0.55A, and the time is 30 minutes.
And step five, obtaining the AlN and CrN enhanced AlCrCuFeNi high-entropy alloy coating after the reaction magnetron sputtering is finished.
Experiments show that the wear-resistant high-entropy alloy coating can be obtained by adopting reactive magnetron sputtering, nitrides AlN and CrN in the coating are fine and uniform, the deformation of a steel matrix is small, and the wear-resistant high-entropy alloy coating can be used for high-precision wear-resistant occasions.
Example 4:
the invention adopts a reactive magnetron sputtering technology to prepare a high-entropy alloy coating, and the preparation method comprises the following process steps:
step one, selecting a steel surface of a precoated workpiece 45 to carry out pretreatment, polishing the surface of the steel surface by using sand paper to remove rust, burrs and flashes, and removing oil stains on the surface by using acetone;
alloying the single-substance metal powder Cr, Cu, Fe, Ni and Al by adopting a ball-milling mixing process, wherein the purity of each single-substance powder is 99.5-100%, and the particle size of the powder is 30-120 mu m; the method comprises the following steps of mixing Cr, Cu, Fe, Ni and Al in a mass ratio of 1:1.3:1.4:1.5:0.6 by ball milling in a steel ball milling tank, sealing, opening a vacuum valve to vacuumize for 25 minutes, putting the steel ball milling tank into a planetary ball mill at a rotating speed of 310 r/min and a reverse frequency of 41 Hz, and mixing the materials by ball milling for 72 minutes, wherein the mass ratio of grinding balls to metal powder is 2.9: 1. And then, putting the powder into a pressure sintering furnace under the protection of argon, pressurizing to 280MPa, keeping the temperature for 5 minutes at the sintering temperature of 1010 ℃, and sintering to obtain the high-entropy alloy target.
Thirdly, placing the high-entropy alloy target on a direct current cathode of the magnetron sputtering equipment, closing a vacuum chamber of the magnetron sputtering equipment, and vacuumizing to 8 × 10-3And Pa, introducing the flow of the Ar gas-regulated gas flowmeter to stabilize the gas pressure within the range of 1-2 Pa, turning on a negative bias power supply, regulating the negative bias to the range of 450V, and carrying out ion bombardment glow cleaning on the pre-coated workpiece for 15 minutes.
And step four, starting a heater of the magnetron sputtering equipment to heat the precoated workpiece after cleaning, and introducing 20 liters/minute of argon and nitrogen mixed gas into the vacuum chamber, wherein the argon: the flow ratio of nitrogen is 1:2.2, the working air pressure is kept between 0.3Pa and 0.5 Pa, the target spacing is kept between 35mm, the temperature of the precoated workpiece is kept at 200 ℃, the substrate bias voltage is 0.35 kV, the sputtering current is 0.25A to 0.3A, and the magnetron sputtering time is controlled to be 16 minutes.
And step five, obtaining the AlN and CrN enhanced AlCrCuFeNi high-entropy alloy coating after the reaction magnetron sputtering is finished.
Experiments show that the wear-resistant high-entropy alloy coating can be obtained by adopting reactive magnetron sputtering, nitrides AlN and CrN in the coating are fine and uniform, the deformation of a steel matrix is small, and the wear-resistant high-entropy alloy coating can be used for high-precision wear-resistant occasions.
Claims (3)
1. A method for preparing a high-entropy alloy coating based on a reactive magnetron sputtering technology is characterized by comprising the following process steps:
the method comprises the following steps of firstly, pretreating the surface of a precoated workpiece, namely polishing the surface by using a grinding wheel or abrasive paper to remove rust, burrs and flashes, and removing oil stains on the surface by using acetone;
alloying the single-substance metal powder Cr, Cu, Fe, Ni and Al according to a certain proportion by adopting a ball-milling mixing process, and then preparing the high-entropy alloy target by adopting pressure sintering, wherein the purity of the single-substance metal powder Cr, Cu, Fe, Ni and Al is 99.5-100%, and the particle size of the powder is 30-120 mu m; the mass ratio of Cr, Cu, Fe, Ni and Al is 1-1.1: 1.2-1.3: 1.2-1.4: 1.3-1.5: 0.5-0.6; the pressure sintering process comprises the following steps: pressurizing in a pressurizing sintering furnace under the protection of argon for 200-350 MPa, wherein the sintering temperature ranges from 950-1070 ℃, and preserving heat for 2-8 minutes;
step three, placing the high-entropy alloy target on a direct current cathode of a magnetron sputtering device, closing a vacuum chamber of the magnetron sputtering device, vacuumizing and filling argon gas, and then performing ion cleaning, wherein the specific process is that the vacuum chamber of the magnetron sputtering device is vacuumized to 2.1 × 10-2Pa~2×10-3Pa, introducing the flow of an Ar gas-regulating gas flowmeter to stabilize the gas pressure within the range of 1-6 Pa, turning on a negative bias power supply, regulating the negative bias to the range of 450-900V, and performing ion bombardment glow cleaning on the pre-coated workpiece for 10-20 minutes;
step four, starting a heater of the magnetron sputtering equipment after cleaning, heating the precoated workpiece, and performing reactive magnetron sputtering, wherein the specific process comprises the following steps: introducing 10-45L/min of argon and nitrogen mixed gas into a vacuum chamber of the magnetron sputtering equipment, wherein the argon: the flow ratio of nitrogen is 1: 2.1-3.2, the working air pressure is kept at 0.3-4.5 Pa, the target spacing is kept at 30-65 mm, the temperature of the precoated workpiece is kept at 190-210 ℃, the substrate bias voltage is 0.3-0.4 kV, the sputtering current is 0.1-0.75A, and the sputtering time is controlled for 5-36 minutes;
and step five, obtaining the AlN and CrN enhanced AlCrCuFeNi high-entropy alloy coating after the reaction magnetron sputtering is finished.
2. The method for preparing the high-entropy alloy coating based on the reactive magnetron sputtering technology as claimed in claim 1, characterized in that: the precoated workpiece is made of steel.
3. The method for preparing the high-entropy alloy coating based on the reactive magnetron sputtering technology as claimed in claim 1, characterized in that: the ball milling mixing is carried out by adopting a steel ball milling tank, wherein the mass ratio of milling balls to metal powder is 2.6-3: 1, a vacuum valve is opened after sealing, vacuum pumping is carried out for 20-30 minutes, then the steel ball milling tank is placed into a planetary ball mill, the rotating speed is 260-320 r/min, the inversion frequency is 35-45 Hz, and the ball milling mixing time is 60-80 minutes.
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| CN111411319B (en) * | 2020-03-01 | 2022-03-18 | 苏州科技大学 | Method for preparing nitride-enhanced high-entropy alloy coating by plasma cladding |
| CN112921267B (en) * | 2020-06-08 | 2023-06-09 | 自贡市量子金属制造有限公司 | TiVZrCrAl high-entropy alloy coating on ball valve round head surface and preparation method thereof |
| CN111676361A (en) * | 2020-07-20 | 2020-09-18 | 安徽省巢湖市共力链条有限公司 | Heat treatment process for high-strength corrosion-resistant chain |
| CN114318208B (en) * | 2022-01-07 | 2023-12-08 | 中国科学院合肥物质科学研究院 | Composite coating for lead-based reactor pump impeller and preparation method thereof |
| CN114875373A (en) * | 2022-05-18 | 2022-08-09 | 上海大学 | High-entropy ceramic composite coating preparation method based on magnetron sputtering and high-entropy ceramic composite coating |
| CN115305444B (en) * | 2022-07-06 | 2023-09-05 | 成都理工大学 | Zirconium alloy-based AlCrNbTiZr high-entropy alloy coating resistant to high-temperature water corrosion and preparation method thereof |
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